Photographic silver halide emulsion sensitized with a methine dye

ABSTRACT

Novel cyanine and merocyanine dyes are provided which feature a nucleus selected from the group consisting of a 1-(3,-4,4a,5,6,7hexahydro-2-naphthyl)pyrrolidine group, a 1-(3,3a,4,5-tetrahydro2H-inden-6-yl)pyrrolidine group, a 1-(2-norbornylidene)pyrrolidine group, and a 1-(1-indanylidene)pyrrolidine group.

United States Patent Fumia, Jr. et al.

[151 3,655,392 1 Apr.1l,1972

[54] PHOTOGRAPHIC SILVER HALIDE EMULSION SENSITIZED WITH A METHINE DYE[72] Inventors: Arthur Fumia, Jr., Hilton; Leslie G. S.

Brooker, Rochester, both of NY.

[73] Assignee: Eastman Kodak Company, Rochester,

[22] Filed: June 4, 1969 [2]] Appl. No.: 830,483

[52] US. Cl ..96/131 [51] Int. Cl ..G03c 1/08 [58] Field ofSearch..96/131,l36

[56] References Cited UNITED STATES PATENTS 2,956,881 10/1960 Van Lare..96/l02 FOREIGN PATENTS OR APPLICATIONS 674,800 1/1965 Belgium PrimaryExaminer-Norman G. Torchin Assistant Examiner-John L. GoodrowAttorney-W. H. J. Kline, J. R. Frederick and O. H. Webster [5 7]ABSTRACT Novel cyanine and merocyanine dyes are provided which feature anucleus selected from the group consisting of a l-(3,-4,4a,5,6,7-hexahydro-2-naphthyl)pyrrolidine group, a l- (3,3a,4,5-tetrahydro-2H-inden-6-yl)pyrrolidine group, a l-( 2-norbornylidene)-pyrrolidine group, and a l-( l-indanylidene)pyrrolidinegroup.

14 Claims, No Drawings This invention relates to novel methine dyes, andmore particularly to enamine dyes and photographic emulsions andelements. containing these dyes; and, to the preparation of these noveldyes.

A number of methine dyes derived from certain enamine derivatives havingutility as spectral sensitizers for photographic silver halide emulsionshave been previously disclosed. For example, in Belgian Patent No.674,800, dated Jan. 3, 1966, methine dyes derived fromN-cyclopentenyl-pyrrolidine and related enamines are described. However,it has been noted that such prior art dyes tend to be contaminated withbis dyes due to the enamine intermediates having more than one reactiveposition. Dyes entirely free from such bis dye by-products would,therefore, appear to have significant advantages in the preparationprocedure and uses thereof as spectral sensitizers in the photographicart over prior art dyes such as mentioned above.

It is, accordingly, an object of this invention to provide a new classof methine dyes derived from enamines that are free from his typecontaminations.

Another object of this invention is to provide novel photographic silverhalide emulsions containing one or more of the new dyes as spectralsensitizers therefor.

Still another object of this invention is to provide light-sensitivephotographic elements comprising a support having thereon at least onenovel emulsion layer of the invention.

Another object of this invention is to provide means for preparing thesenew dyes and novel photographic materials.

Other objects of this invention will be apparent from this disclosureand the appended claims.

We have now made the important discovery that methine dyes can bederived from certain enamines containing two fused carbocyclic ringsthat form part of the methine chain, and that these dyes are free fromany noticeable bis dye contaminations. These novel dyes are excellentspectral sensitizers for light-sensitive photographic silver halideemulsions up to wavelengths ranging about from 520 to 750 nm., withmaximum sensitivities occuring in the range about from 490 to 700 nm.Thus, these dyes sensitize not only from the blue to the red regions,but in many cases in the near infrared regions of the spectrum. Ingeneral, the novel dyes of this invention cause only very low fog levelin both fresh and incubated emulsions, and the negative images producedwith emulsions containing these dyes are clear and sharp, and ofexcellent contrast.

The novel methine dyes of this invention include those comprising firstand second nuclei joined by a double bond or methine linkage (includingone or more methine groups); the first of said nuclei being selectedfrom the group consisting of (l) a nitrogen containing heterocyclicnucleus of the type used in cyanine dyes having from to 6 non-metallicatoms in the heterocyclic ring, and (2) a nitrogen containingheterocyclic ketomethylene nucleus of the type used in merocyanine dyeshaving from 5 to 6 non-metallic atoms in the hetrocyclic ring, joined ineach instance by a carbon atom of l) or (2) to said linkage; and saidsecond nucleus being an enamine group selected from the group consistingof a l-(3,4,4a,5,6,7-hexahydro-Z-naphthyl)-pyrrolidine group, al-(3,3a,4,5- tetrahydro-2H-inden-6-yl)-pyrrolidine group, al-(2-norbornylidene)pyrroline group and a 1-( l-indanylidene)pyrrolidinegroup, joined at a carbon atom thereof to said linkage, to complete saiddye.

The preferred novel methine dyes of the invention that are particularlyuseful include those represented by the following formulas:

wherein n and d each represents a positive integer of from 1 to 2; mrepresents a positive integer of from 1 to 3; L represents amethinelinkage,e.g., CH-, C(CH C(C6H etc.; D represents an enamine groupselected from a 2,3,4,4a,5 ,6hexahydro-7-( l -pyrrolidinyl)- l -naphthylgroup,

a 2,6,7,7a-tetrahydro-5-( l-pyrrolidinyl)-3-indenyl group, a 3-(1-pyrrolidinyl)-2-norbomen-2-yl group or a 3-(l-pyrrolidinyl)-2-indenylgroup, represented by the following basic structures:

which groups can be further substituted on appropriate nuclear carbonatoms thereof by alkyl, e.g., methyl, butyl, etc., or alkoxy, e.g.,methoxy, butoxy, etc., and the like; R represents an alkyl group,including substituted alkyl, (preferably a lower alkyl containing from 1to 4 carbon atoms),e.g.,methyl,ethyl,propyl, isopropyl,butyLhexyl,cyclohexyl, decyl, dodecyl, etc., and substituted alkylgroups (preferably a substituted lower alkyl containing from one to fourcarbon atoms), such as a hydroxyalkyl group, e. g., B-hydroxyethyl,w-hydroxybutyl, etc., an alkoxy-alkyl group, e.g., ,B-methoxyethyl,w-butoxybutyl, etc., a car-boxyalkyl group, e.g., B-carboxyethyl,w-carboxybutyl, etc.; a sulfoalkyl group, e.g., B-sulfoethyl,w-sulfobutyl,etc., a sulfatoalkyl group, e.g., B-sulfatoethyl,m-sulfatobutyl, etc., an acyloxyalkyl group, e.g., ,B-acetoxyethyl,y-acetoxypropyl, m-butyryloxybutyl, etc., an alkoxycarbonylalkyl group,e.g., B-methoxycarbonylethyl, w-ethoxycarbonylbutyl, etc., or an aralkylgroup e.g., benzyl, phenethyl, etc., or any aryl group,e.g., phenyl,tolyl, naphthyl, methoxyphenyl, chlorophenyl, etc.; X represents an acidanion, e.g., chloride, bromide, iodide, perchlorate, sulfamate,p-toluenesulfonate, methylsulfate, etc., and can be included in R,, suchas when R represents a carboxyalkyl or sulfoalkyl group and the dye isin the form of an internal anhydride; Z represents the non-metallicatoms necessary to complete the same or different 5- to 6-memberedheterocyclic nucleus of the type used in cyanine dyes, which nucleus maycontain a second hetero atom such as oxygen, sulfur, selenium ornitrogen, such as the following nuclei: a thiazole nucleus, e.g.,thiazole, 4-methylthiazole, 4-phenylthiazole, 5-methylthiazole,S-phenylthiazole, 4,5- dimethylthiazole, 4,5-diphenylthiazole,4-(2-thienyl)thiazole, benzothiazole, 4-chlorobenzothiazole,5-chlorobenzothiazole, 6-chlorobenzothiazole, 7-chlorobenzothiazole,4-methylbenzothiazole, S-methylbenzothiazole, 6-methylbenzothiazole,S-bromobenzothiazole, 6-bromobenzothiazole, S-phenylbenzothiazole,S-phenylbenzothiazole, 4-methoxybenzothiazole, S-methoxybenzothiazole,6-methoxybenzothiazole, 5-iodobenzothiazole, 6-iodobenzothiazole, 4-ethoxybenzothiazole, 5-ethoxybenzothiazole, tetrahydrobenzothiazole,5,6-dimethoxybenzothiazole, 5,6- dioxymethylenebenzothiazole,S-hydroxybenzothiazole, 6- hydroxybenzothiazole, naphtho[2,l-d1thiazole,naphtho[ 1,2- d]thiazole, 5-methoxynaphtoh[2,3-d]thiazole,5-ethoxynaphtho[2,3-d]thiazole, 8-methoxynaphtho[2,3-d]thiazole,7-methoxynaphtho[2,3-d]thiazole, 4'-methoxythianaphtheno-7,6,-4,5-thiazole, etc.; an oxazole nucleus, e.g., 4-methyloxazole,S-methyloxazole, 4-phenyloxazole, 4,5-diphenyloxazole, 4-ethyloxazole,4,5-dimethyloxazole, S-phenyloxazole, benzoxa-zole, 5-chlorobenzoxazole,S-methylbenzoxazole, 5- phenylbenzox-azole, -methylbenzoxazole,5,6-dimethylbenzoxazole, 4,6-di-methylbenzoxazole, S-methoxybenzoxazole,S-ethoxybenzoxazole, 5-chlorobenzoxazole, 6-methoxybenzoxazole,S-hydroxybenzoxazole, -hydroxybenzoxazole, naphtho[2,l-d1oxazole,naphtho[l,2-d]-oxazole, etc.; a selenazole nucleus, e.g.,4-methylselenazole, 4-phenylselenazole, benzoselenazole,5-chlorobenzoselenazole, 5-

l0l03l 0142 l,3-diethyl-2,4-imidazolidinedione,

methoxybenzoselenazole, S-hydroxybenzoselenazole,tetrahydrobenzoselenazole, naphtho[ 2, l-dlselenazole,naphtho[l,2-d]selenazole, etc.; a thiazoline nucleus, e.g., thiazoline,4-methylthiazoline, etc.; a pyridine nucleus, e.g,, 2- pyridine,5-methyl-2-pyridine, 4-pyridine, 3-methyl-4- pyridine, etc.; a quinolinenucleus, e.g., 2-quinoline, 3-methyl- Z-quinoline, S-ethyl-Z-quinoline,6-chloro-2-quinoline, 8- chloro-2-quinoline, 6-methoxy-2-quinoline,8-ethoxy-2-quinoline, 8-hydroxy-2-quinoline, 4-quinoline,6-methoxy-4-quinoline, 7-methyl-4-quinoline, 8-chloro-4-quinoline,l-isoquinoline, 3,4-dihydro-lisoquinoline, 3-isoquinoline, etc., a 3,3-dialkylindolenine nucleus, e.g., 3,3-dimethylinolenine, 3,3,5-trimethylindolenine, etc.; and, an imidazole nucleus, e.g., imidazole,l-alkylimidazole, l-alkyl-4-phenylimidazole,lalkyl'4,5-dimethylimidazole, benzimidazole, l-aikylbenzimidazole,l-aryl-S ,6-dichlorobenzimidazole, l-alkyll H- naphth[ l,2-d]imidazole,1-aryl-3l-l-naphth[ l,2-d]imidazole,l-alkyl-5-methoxy-ll-l-naphth-[l,2-d]imidazole, etc; and Q representsthe non-metallic atoms necessary to complete a 5- or 6-membered nucleus,of the type used in merocyanine dyes typically containing a hetero atomselected from nitrogen, sulfur, selenium, and oxygen, such as aZ-pyrazoline-S-one nucleus, e.g., 3-methyl-l-phenyl-2-pyrazolin-5-one,l-phenyl- 2-pyrazolin-5'one, l-(Z-benxothiazolyl)-3-methyl-2-pyrazolimS-one, etc.; an isoxazolone nucleus, e.g., 3-phenyl-5(4H)-isoxazolone, 3-methyl-5(4H)-isoxazolone, etc.; an oxindolenucleus, e.g., l-alkyl-Z-oxindoles, etc.; a 2,4,6-triketohexahydropyrimidine nucleus, e.g., barbituric acid or2-thiobarbituric acid as well as their l-alkyl (e.g., l-methyl, lethyl,l-propyl, l-heptyl, etc.) or l,3-dialkyl(e.g., 1,3- dimethyl,1,3-diethyl, 1,3-di-propyl, 1,3-diisopropyl, 1,3- dicyclohexyl,l,3-di(fl-methoxyethyl), etc.; or 1,3-diaryl (e.g., 1,3-diphenyl,1,3-di-(p-chlorphenyl), l,3-di(p-ethoxycarbonylphenyl), etc.); or l-aryl(e.g., l-phenyl, l-p-chlorophenyl, lp-ethoxycarbonylphenyl), etc.) orl-alkyl-3-aryl (e.g., l-ethyl- B-phenyl, l-n-heptyl-B-phenyl, etc.)derivatives; a rhodanine nucleus (i.e., 2-thio-2,4-thiazolidinedioneseries), such as rhodanine, 3-alkylrhodanines, e.g., B-ethylrhodanine,3-allylrhodanine, etc., 3-carboxyalkylrhodanines, e.g.,3-(2-carboxyethyl)rhodanine, 3-(4-carboxybutyl)rhodanine, etc.,3-sulfoalkylrhodanines, e.g., 3-(2-sulfoethyl)rhodanine,3-(3-sulfopropyl)rhodanine, 3-(4-sulfobutyl)rhodanine, etc., or 3-arylrhodanines, e.g., 3- phenylrhodanine, etc., etc.; a 2(3H)-imidazo[l,2-a]pyridone nucleus; a 5,7-dioxo-6,7-dihydro-5-thiazolo[3,2-a]pyrimidine nucleus, e.g., 5,7-dioxo-3-phenyl-6,7-dihydro-5-thiazolo[3,2-a]-pyrimidine, etc.; a 2-thio-2,4-oxazolidinedione nucleus (i.e., those of the 2-thio-2,4(3H,5l-l)-oxazoledione series) e.g.,3-ethyl-2-thio-2,4-oxazolidinedione,3(2-sulfoethyl)-2thio-2,4-oxazolidinedione,3-4-sulfobutyl)-2-thio-2,4-oxazolidinedione, 3-(3-carboxypropyl)-2-thio-2,4-oxazolidinedione, etc.; a thianaphthenonenucleus, e.g., 3-(2l-l)-thianaphthenone, etc.; a 2-thio-2,5-thiazolidinedione nucleus (i.e., the 2-thio-2,5-(3l-l,4l-l)-thiazoledione series), e.g., 3-ethyl-2-thio-2,5- thiazolidinedione, etc;a 2,4-thiazolidinedione nucleus, e.g., 2,4-thiazolidinedione,3-ethyl-2,4-thiazoiidinedione, 3-phenyl-2,4-thiazolidinedione,3-a-naphthyl-2,4-thiazolidinedione, etc; a thiazolidinone nucleus, e.g.,4-thiazolidinone, 3-ethyl- 4-thiazolidinedione3-phenyl-4-thiazolidinone, 3-a-naphthyl-4 -thiazolidinone, etc; a2-thiazoline-4-one nucleus, e.g., 2- ethylmercapto-2-thiazoline-4-one,2-alkylphenylamino-2- thiazolin-4-one,2-diphenylamino-2-thiazolin-4-one, etc; a 2- imino-4-oxazolidinone(i.e., pseudohydantoin) nucleus; a 2,4- imidazolidinedione (hydantoin)nucleus, e.g., 2,4- imidazolidinedione, 3-ethyl-2,4-imidazolidinedione,3-phenyl- 2,4-imidazolidinedione, 3-a-napthyl-2,4-imidazolidinedione,

l-ethyl-3-phenyl-2,4- imidazolidinedione, l-ethyl-3-a-naphthyl-2,4-imidazolidinedione, l,3-diphenyl-2,4-imidazolidinedione, etc; a2-thio-2,4-imidazolidinedione (i.e., 2-thiohydantoin) nucleus, e.g.,2-thio-2,4-imidazolidinedione, 3-ethyl-2-thio- 2,4-imidazolidinedione,3-(4-sulfobutyl)-2-thio-2,4 imidazolidinedione,3-(2-carboxyethyl)-2-thio-2,4-

imidazolidinedione, 3-phenyl-2-thio-2,4-imidazolidinedione,3-a-naphthyl-2-thio-2,4-imidazolidinedione, l ,l ,3-diethyl-2- thio-2,4-imidazolidinedione, l-ethyl-3-phenyl-2-thio-2,4- imidazolidinedione,l-ethyl-3-a-naphthyl-2-thio-2,4- imidazolidinedione, l,3-diphenyl-2-thio-2,4- imidazolidinedione, etc.; a Z-imidazolinl-S-onenucleus, e.g., 2 propylmercapto-2-imidazolin-5-one, etc.; etc.(Especially useful are nuclei wherein Q represents the non-metallicatoms required to complete a heterocyclic nucleus containing five to sixatoms in the heterocyclic ring, three to four of said atoms beingcarbon, and two of said atoms being selected from the group consistingof nitrogen, oxygen, and sulfur, and at least one of said two atomsbeing a nitrogen atom.

The novel methine dyes of this invention can be conveniently prepared ina number of ways. For example. a number of the dyes defined by Formula 1above are advantageously prepared by heating a mixture of (l) aheterocyclic salt of the formula:

wherein m is 2 or 3, n, L, R,, X and Z are previously defined, and Rrepresents a hydrogen atom or an acyl group, e.g., acetoxy, phenoxy,etc,, with (2) an enamine intermediate selected from the groupconsisting of a l-(3,4,4a,5,6,7-hexahydro-Z-naphthyl)-pyrrolidine, or al(3,3a,4,5-tetrahydro- 2l-l-inden-6-yl)pyrrolidone, or al-(2-norbornylidene)pyrrolidinium salt, e.g., the chloride, bromide,iodide, perchlorate, p-toluenesulfonate, etc. salt, or al-(l-indanylidene)pyrrolidinium salt, e.g., the chloride, bromide,iodide, perchlorate, p-toluenesulfonate, etc. salt, in approximatelyequimolar proportions, in a solvent medium such as ethanol, pyridine,N,N-dimethylacetamide, acetic anhydride, etc. Advantageously, a basiccondensing agent such as triethylamine is used with the acetic anhydridereaction medium. The dyes are then separated from the reaction mixturesand purified by one or more recrystallizations from appropriate solventssuch as methanol, mixtures of pyridine and methanol, and the like. Thedyes wherein the value of m is 1 in Formula 1 above are advantageouslyprepared with (l) a heterocyclic salt of the formula:

IV. I .z

In the preparation of photographic emulsions, the new dyes of theinvention are advantageously incorporated in the finished silver halideemulsion and should, of course, be uniformly distributed throughout theemulsion. The methods of incorporating dyes in emulsions are relativelysimple and well known to those skilled in the art of emulsion making.For

example, it is convenient to add the dyes from solutions in appropriatesolvents, in which the solvent selected should have no deleteriouseffect on the ultimate light-sensitive materials. Methanol, isopropanol,pyridine, etc., alone or in combination have proven satisfactory assolvents for the majority of our new dyes. The type of silver halideemulsions that are sensitized with our dyes include any of thoseprepared with hydrophilic colloids that are known to be satisfactory fordispersing light-sensitive silver halides, for example, emulsionsprepared with hydrophilic colloids, such as, natural materials, e.g.,gelatin, albumin, agar-agar, gum arabic, alginic acid, etc., andsynthetic hydrophilic resins, e.g., polyvinyl alcohol, polyvinylpyrrolidone, cellulose ethers, partially hydrolyzed cellulose acetate,and the like.

The concentration of our new dyes in the emulsion can be widely varied,i.e., generally from about 5 to about 100 mg. per liter of flowableemulsion. The specific concentration will vary according to the type oflight-sensitive material in the emulsion and according to the effectsdesired. The most advantageous dye concentration for any given emulsioncan be readily determined by making the tests and observationscustomarily used in the art of emulsion making. The dyes of theinvention can be used alone, in combination with each other or incombination with other sensitizing dyes. The emulsions are coated toadvantage on any of the support materials used for photographicelements, for example, paper, glass, cellulose acetate, celluloseacetate-propionate, cellulose nitrate, polystyrene, polyesters,polyamides, etc.

To prepare a gelatino-silver halide emulsion sensitized with one of thenew dyes, the following procedure is satisfactory: A quantity of the dyeis dissolved in a suitable solvent and a volume ofthis solutioncontaining from 5 to 100 mgs. of dye is slowly added to about 1000 cc.of a gelatino-silver halide emulsion. With most of the new dyes, 10 tomgs. ofdye per liter of emulsion suffice to produce the maximumsensitizing effect with the ordinary gelatino-silver halides includingsilver chloride, bromide bromoiodide, chlorobromide, chlorobromoiodide,etc. emulsions. With fine-grain emulsions, which include most of theordinary employed gelatinosilver chloride emulsions and the like,somewhat larger concentrations of dye may be necessary to secure optimumsensitizing effect. While the preceding has dealt with emulsionscomprising gelatin, it will be understood that these remarks applygenerally to any emulsions wherein part or all of the gelatin issubstituted by another suitable hydrophilic colloid such as mentionedabove.

The above statements are only illustrative and are not to be understoodas limiting the invention in any sense, as it will be apparent that thenew dyes can be incorporated by other methods in many of thephotographic silver halide emulsions customarily employed in the art.For instance, the dyes can be incorporated by bathing a plate or filmupon which an emulsion has been coated, in the solution of the dye in anappropriate solvent. Bathing methods, however, are not to be preferredordinarily.

Photographic silver halide emulsions, such as those listed above,containing the sensitizing dyes of my invention can also contain suchaddenda as chemical sensitizers, e.g., sulfur sensitizers (e.g., allylthiocarbamide, thiourea, allylisothiocyanate, cystine, etc.), variousgold compounds (e. g., potassium chloroaurate, auric trichloride, etc.)(see U.S. Pats. Nos. to W. D. Baldsiefen 2,540,085, granted Feb. 6,1951; R. E. Damschroder 2,597,856, granted May 27, 1952, and H. C. Yutzyet a1. 2,597,915, granted May 27, 1952), various palladium compounds,such as palladium chloride (W. D. Baldsiefen U. S. Pat. No. 2,540,086,granted Feb. 6, 1951), potassium chloropalladate (R. E. Stauffer et a1U. S. Pat. No. 2,598,079, granted May 27, 1952), etc., or mixture ofsuch sensitizers; antifoggants, such as ammonium chloroplatinate (A. P.H. Trivelli et al. U. S. Pat. No. 2,566,245, granted Aug. 28, 1951),ammonium chloroplatinite (A.P.l-1. Trivelli et al. U.S. Pat. No.2,566,263, granted Aug. 28, 1951), benzotriazole, nitrobenzimidaz ole,S-nitroindazole, benzidine,

mercaptans, etc. (see Mees, The Theory of the Photographic Process,Macmillan Pub., 1942, page 460), or mixtures thereof; hardeners, such asformaldehyde (A. Miller U.S. Pat. No. 1,763,533, granted June 10, 1930),chrome alum (U.S. Pat. No. 1,763,533), glyoxal (J. Brunken U. 8. Pat.No. 1,870,354, granted Aug. 9, 1932, dibromacrolein (0. Block et al.British Pat. No. 406,750, accepted Mar. 8, 1934), etc., color couplers,such as those described in 1. F. Salminen et al. U. S. Pat. No.2,423,730, granted July 7, 1947, Spence and Carroll U. S. Pat. No.2,640,776, issued June 2, 1953, etc.; or mixtures of such addenda.Dispersing agents for color couplers, such as those set forth in U. S.Pats. Nos. to E. E. Jelley et al. 2,322,027, granted June 15, 1943, andL. D. Mannes et al. 2,304,940, granted Dec. 15, 1942, can also beemployed in the above-described emulsions.

The following examples further illustrate the novel dyes andphotographic materials of this invention.

Example 13-ethyl-2-12-[2,3,4,4a,5,6-hexahydro-7-(l-pyrr0lidinyl)-1-naphthyl]vinyllbenzoxazolium iodide 1-(3,4,4a,5,6,7-hexahydro-2-naphthyl)pyrrolidine(2.0 g.) and 2-(2-acetanilidovinyl)-3-ethylbenzoxazolium iodide (4.3 g.)are dissolved in ethanol (15 ml.) and heated at reflux for 10 minutes.After chilling, the crude dye is collected on a filter and dried. Afterone recrystallization from methanol, the yield ofpurified dye is 1.8 g.(36 percent), m.p. 212-213 C., dec.

Example 2 CzHs 1-( 3 ,4,4a,5 ,6,7-hexahydro-2-naphthyl)pyrrolidine (2.0g.) and 2-(2-acetanilidovinyl)3-ethylbenzothiazolium iodide (4.5 g.) aredissolved in ethanol (15 ml.) and heated at reflux for 10 minutes. Afterchilling, the crude dye is collected on a filter and dried. After onerecrystallization from methanol, the yield of purified dye is 1.8 g. (35percent), m.p. 240-241 C. dec.

Example 3 ene)rhodarune C li;

l O&S CH

1-( 3 ,4,4a,5,6,7-hexahydro-2-naphthyl)pyrrolidine (2.0 g. and-acetanilidomethylene-3-ethylrodanine (3.1 g.) are dissolved in ethanol(15 m1.) and heated at reflux for 3 minutes. After chilling, the crudedye is collected on a filter and dried. After one recrystallization frompyridine/methanol, the yield of purified dye is 2.0 g. (54 percent), m.p. 198199 C. dec.

Example 4 3-ethyl-2-[2,6,7,7a-tetrahydro-5-(1-pyrro11dinyD-3-lndenyllbenzethiazollum perchloratel-( 3,3a,4,5-tetrahydro-2H-iden-6-y1)pyrrolidone 1.9 g.) and3-ethy1-Z-phenylthiobenzothiazolium iodide (4.0 g.) are dissolved inethanol (15 ml.) and heated at reflux for 5 minutes. A hot aqueoussolution ml.) of NaClO 1.8 g.) is then added. After chilling, the crudedye is collected on a filter and recrystallized fromN,N-dimethylacetamide/methanol. The yield of purified dye is 0.9 g. (20percent) m.p. 27027 1 C. dec.

Example 5 3-ethyl-2-[2-[2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-lndenyl]vlnyl) benzoxazolium iodide CzH 1-(3,3a,4,5-tetrahydro-2l-l-inden-6-y1)pyrrolidine 1.9 g.) and2-(2-acetanilidovinyl)-3-ethylbenzoxazo1ium iodide (4.3 g.) aredissolved in ethanol ml.) and heated at reflux for 5 minutes. Afterchilling, the crude dye is collected on a filter and dried. After onerecrystallization from methanol, the yield of purified dye is 2.3 g. (47percent), m.p. 258259 C. dec.

Example 6 3-ethyl-2- l 2-[2,6 ,7 ,7atetrahydro-5-( l-pyrrolldinyl)-3-indenyl] vinyl) benzothiazollurn iodide 1-(3,3a,4,5-tetrahydro-2H-inden-6-yl)pyrrolidine 1 .9 g.) and2-(Z-acetanilidovinyl)-3-ethylbenzothiazolium iodide (4.5 g.) aredissolved in ethanol (15 ml.) and heated at reflux for 5 minutes. Afterchilling, the crude dye is collected on a filter and dried. After onerecrystallization from methanol, the yield of purified dye is 2.1 g. (42percent), m.p. 252-253 C. dec.

Example 7 3-heny1-4-{[2,6,7,7a-tetrahydro-5-(l-pyrrolidinyl)-3-lndenyl]methylene) 2-soxazolin-5-one Example 8 3-methyl'1-phenyl-4- [2,6,7,7a-tetrahydro-5-(1 -pyrro11dinyl) -3-indenyl] 5 5 methylene} -2-pyrazolin-5-one4-Anilinomethylene-3-methyll-phenyl-2-pyrazoline'5-one (2.8 g.) andl-(3,3a,4,5-tetrahydro-2l-l-inden-6-yl)-pyrrolidine (1.9 g.) arecondensed in N,N-dimethylacetamide (15 ml.) with acetic anhydride (1.0ml.) and triethylamine (1.5 ml.) in the manner as in Example 7. Afterone recrystallization from pyridine/methanol, the yield of purified dyeis 0.8 g. (22 percent), m.p. 220-221C. dec.

Example 103-ethyl-2-12-[3-(1-pyrro1ldiny1)-2-norbornen-2-y1]v1nyl1benzoxazollumperchlorate 1-(Z-Norbomylidene)pyrrolidinium perchlorate (2.6 g.), 2-(Z-acetanilidovinyl)-3-ethylbenzoxazo1ium iodide (4.3 g.), andtriethylamine (1.5 ml.) are dissolved in acetic anhydride ml.) andheated at reflux with stirring, for 5 minutes. After cooling, ether (200ml.) is added with stirring. Decanted, stirred residue with water (150ml.) and decanted. The residue is then stirred with a little warmethanol and crystals formed. After chilling, the solid is collected on afilter and dissolved in ethanol. After chilling, the mixture is filteredto remove unwanted material. The filtrate is concentrated to 50 ml. andchilled. The dye is then collected on a filter and dried. The yield is0.7 g. (16 percent), m.p. l96l97C. dec.

Example 1 13-ethyl-2-12-[3-(1pyrrolld1nyl)-2-norbornen-2-yl1v1nyl)benzothlazollumperchlorate 1-(2-Norbornylidene)pyrrolidinium perchlorate (2.6 g.), 2-(2-acetanilidovinyl)-3-ethylbenzothiazolium iodide (4.5 g.), andtriethylamine (1.5 ml.) are dissolved in acetic anhydride (15 ml.) andheated at reflux, with stirring, for 5 minutes. After cooling, ether(200 ml.) is added with stirring. The liquid is decanted and the residuestirred with a fresh portion of ether (200 ml.), decanted and then theresidue dissolved in ethanol, discarding some material that does notreadily dissolve. After chilling, the solid is collected on a filter anddried. The yield is 1.2 g. (27 percent). The crude dye is recrystallizedfrom methanol, with the hot solution being passed through a bed ofNorite. The yield of purified dye is 0.6 g. (13 percent), m.p. 231-232C.dec.

1-(2-Norbornylidene)pyrrolidinium perchlorate (2.6 g.), 2-(ani1inovinyl)-1-ethylnaphtho[ 1,2-d1thiazolium p-toluenesulfonate (5.0g.), acetic anhydride (1.0 ml.), and triethylamine (3.1 ml.) aredissolved in N,N-dimethy1acetamide (15 ml.) and heated at reflux, withstirring for 5 minutes. The hot reaction mixture is diluted to 300 ml.with boiling methanol and then cooled to room temperature. After onerecrystallization from N,N-dimethylacetamide/methanol, the dye is notpure. The dye is then combined with the recrystallization liquors andmethanol added so as to have a total volume of 800 ml. The mixture isthen heated to reflux and filtered (gravity). The filtrate is thenheated to reflux and the solution is passed through a bed of Norite. TheNorited solution is then heated to reflux and filtered (gravity). Afterconcentrating to 400 ml., the solution is chilled, the dye collected ona filter and dried. The yield of purified dye is 1.6 g. (32 percent),m.p. 262263 C. dec.

Example 13 3-ethyl-2-12-[3-(l-pyrrolldinyl)-Z-1ndeny1jviny11benzoxazoltum (34 percent), m.p. 240-24lC. dec.

Example 14 3-ethy1-2-12-[3-(1-pyrro11dlnyl)-2-indenyl]vinyl) benzothlazollum perchlorate l-(1-Indanylidene)pyrrolidinium perchlorate (2.9 g.),2- (2-acetani1idoviny1)-3-ethylbenzoxazolium iodide (4.3 g.), andtriethylamine (1.5 m1.) are dissolved in pyridine (15 ml.)

- and heated at reflux, with stirring for 10 minutes. After chilling,the solid is collected on a filter, washed with methanol and dried. Thecrude yield is 3.0 (65 percent). After two recrystallizations frompyridine, the yield of purified dye is 1.1 g. (24 percent), m.p.279-280C. dec.

Example 15 L.) is 1) I Example 161-ethy1-2-(2[3-(l-pyrrolldinyl)-2-norbornen-2-y1]viny11naphthofl ,2-d]thiazolium perchlorate [Meg] l-(1-1ndany1idene)pyrrolidinium perchlorate(2.9 g.), 2-( 2- ani!inoviny1)- l-ethy1naphtho[ l ,2-d]thiazoliump-toluene sulfonate (5.0 g.), acetic anhydride (1.0 m1.), andtriethylamine (2.8 m1.) are dissolved in pyridine (25 ml.) and heated atreflux, with stirring, for 5 minutes. After chilling, the solid iscollected on a filter, washed with methanol and dried. The crude yieldis 4.6 g. (88 percent). After two recrystallizations fromcresol/methanol, the yield of purified dye is 3.0 g. (58 percent), m.p.287-288C. dec.

The dyes prepared as described in the above examples are tested in asilver bromoiodide emulsion containing 0.77 mole percent iodide of thetype described by Trivelli and Smith, Phat. Journal, 79, 330 (1939). Thedyes, dissolved in suitable solvents, are added to separate portions ofthe emulsion at the concentrations indicated. After digestion at 52 C.for minutes, the emulsions are coated at a overage of 432 mg. of silverper square foot on a cellulose acetate film support. A sample of eachcoating is exposed on an Eastman 13 Sensitometer and to a edgespectrograph, processed for 3 minutes in Kodak developer D-19 which hasthe following composition:

N-methyl-p-aminophenol sulfate 2.0 g. Hydroquinone 8.0 g. Sodium sulfile(desiccated) 90.0 g. Sodium carbonate (monohydrnte) 52.5 g. Potassiumbromide 5.0 g. Water to make 10 liter and then fixed in a conventionalsodium thiosulfate fixing bath, washed and dried. The sensitizing valuesobtained are shown in Table 1 immediately below.

- Table I Dye of Dye Conc. Sensitization Sensitization Example (gjmoleAg.) Range (nm.) Max. (am) 10 0.04 to 540 S00 12 0.04 to 620 SS0 Theresults shown in above Table 1 indicate that all of the dyes of thepreceding examples are excellent spectral sensitizers forlight-sensitive photographic silver halide emulsions of the negativetype. It is to be noted that in some instances the sensitivity of thetest emulsion is extended into the near infrared regions of thespectrum.

The following examples illustrate the preparation of certain fusedcarbocyclic enamine intermediates that are employed in the precedingexamples.

Example 17 1:( 3a,4,5-Tetrahydro-21-l-inden-6-yl)pyrrolidine1-(3,3a,4,lS-Tetrahydro-2H-inden-6-y1)pyrrolidine To a solution ofN-cyclopentenylpyrrolidine (41.1 g.) in toluene (250 m1.) is added3-buten-2-one (21.0 g.) dropwise. The mixture is then heated at refluxfor 15 hours. The water that forms is azeotroped, the toluene removedunder reduced pressure and the residue distilled under vacuum. The yieldof product is 26.2 g. (46 percent), b.p. 109C./0.09 mm. Hg.

Example 18 1-( 2-Norbomylidene )pyrrolidinium perchlorate 2-Norbornanone1 1.0 g.) and pyrrolidine hydroperchlorate (17.1 g.) are dissolved inethanol (50 ml.). Pyrrolidine (1 drop) is added and the mixture isstirred for 10 minutes. The solid is collected on a filter, rinsedthoroughly with ethanol and dried. The yield is 19.9 g. (75 percent),m.p. 226-227C.

13 Example 19 l-lndanone (22.0 g.), pyrrolidinium hydroperchlorate (22.5g.) and pyrrolidine (4 drops) are dissolved in ethanol (75 ml.) andheated at reflux for 1 hour. After chilling, the solid is collected on afilter, rinsed with ethanol and dried. The yield is 24.7 g. (66percent), m.p. 208-209C.

The preparation of the intermediatel-(3,4,4a,5,6,7-hexahydro-2-naphthyl)pyrrolidine is described by Storket al, J. Amer. Chem. Society, 85, 218 (1963).

It will be apparent from all of the foregoing description and examples,that still other novel dyes of the invention embraced by Formulas l andII above can be prepared by appropriate selection of the heterocyclicand enamine type intermediates, and that these dyes likewise willfunction as effective spectral sensitizers for light-sensitive negativephotographic silver halide emulsions.

Other dyes which are useful in the practice of this invention and can beprepared by the procedures described above, include 3-ethyl-5-[2,3,4,4a,5,6-hexahydro-7-(1'pyrrolidinyl)-l-naphthyl]allylidene}rhodanine; 3-ethyl-2-{2-[ ,6,7,7atetra-hydro--(l-pyrrolidinyl)-3-indenyl]butadieny1 benzothiazolium iodide; l-phenyl-Z-2-[3-(l-pyrrolidinyl)-2- norbornen-2-yl1vinyl -naphtho[ l,2-d]thiazoliumperchlorate; and l-ethyl-4-{ 2-[ 3-( 1-pyrrolidinyl)-2-indenyl]vinylquinoxalinium perchlorate.

The invention has been described in detail with particular reference topreferred embodiments thereof, but, it will be understood thatvariations and modifications can be effected within the spirit and scopeof the invention.

We claim:

1. A light-sensitive photographic silver halide emulsion spectrallysensitized with a methine dye comprising first and second nuclei joinedby a linkage selected from the group consisting of a double bond andmethine linkage; the first of said nuclei being selected from the groupconsisting of (l) a nitrogen containing heterocyclic nucleus having from5 to 6 atoms in the heterocyclic ring, and (2) a nitrogen containingheterocyclic ketomethylene nucleus having from five to six atoms in theheterocyclic ring, said first nucleus being joined by a carbon atomthereof to said linkage; and said second nucleus being an enamine groupselected from the group consisting of al-(3,4,4a,5,6,7-hexahydro-2-naphthyl)pyrrolidine group, al-(3,3a,4,5-tetrahydro-2H-inden-6-yl)pyrrolidine group, al-(2-norbornylidene)pyrrolidine group and a l-(1-indanyliderie)-pyrrolindine group, joined at a carbon atom thereof tosaid linkage.

2. A light-sensitive photographic silver halide emulsion spectrallysensitized with a methine dye having at least one of the followingformulas:

and

wherein d and 11 each represents a positive integer of from 1 to 2; mrepresents a positive integer of from 1 to 3; L represents a methinelinkage; D represents an enamine group selected from the groupconsisting of a 2,3,4,4a,5,6-hexahydro-7-(lpyrrolidinyl)-l-naphthylgroup; a 2,6,7,7a-tetrahydro-5-( lpyrrolidinyl)-3-indenyl group; a3-(l-pyrrolidinyl)-2-norbornen-Z-yl group; and a3-(l-pyrrolidinyl)-2-indenyl group; R represents a member selected fromthe group consisting of an alkyl group and an aryl group; X representsan acid anion; Z represents the non-metallic atoms necessary to completea heterocyclic nucleus containing from five to six atoms in theheterocyclic ring; and Q represents the non-metallic atoms to complete anitrogen containing heterocyclic ketomethylene nucleus containing fromfive to six atoms in the heterocyclic ring.

3. A light-sensitive photographic silver halide emulsion spectrallysensitized with a methine dye represented by the following formula:

wherein n represents a positive integer of from 1 to 2; m represents apositive integer of from 1 to 3; L represents a methine linkage; Drepresents an enamine group selected from the group consisting of a2,3,4,4a,5,6-hexahydro-7-(lpyrrolidinyl)-l-naphthyl group; a2,6,7,7a-tetrahydro-5-('lpyrrolidinyl)-3-indenyl group; a3-(l-pyrrolidinyl)-2-norbornen-2-yl group; and a 3-(l-pyrrolidinyl)-2-indenyl group; R represents a member selected from thegroup consisting of an alkyl group and an aryl group; X represents anacid anion; and Z represents the non-metallic atoms necessary tocomplete a heterocyclic nucleus containing from five to six atoms in theheterocyclic ring.

4. A light-sensitive photographic silver halide emulsion spectrallysensitized with a dye as defined in claim 4 wherein said Z representsthe non-metallic atoms necessary to complete a thiazole nucleus.

5. A light-sensitive photographic silver halide emulsion spectrallysensitized with a dye as defined in claim 3 wherein said Z representsthe non-metallic atoms necessary to complete an oxazole nucleus.

6. A light-sensitive photographic silver halide emulsion spectrallysensitized with a dye as defined in claim 3 wherein said 2 representsthe non-metallic atoms necessary to complete a 3,3-dialkylindoleninenucleus.

7. A light-sensitive photographic silver halide emulsion spectrallysensitized with a methine dye represented by the following formula:

wherein d represents a positive integer of from 1 to 2; L represents amethine linkage; D represents an enamine group selected from the groupconsisting of a 2,3,4,4a,5,6-hexahydro-7 -(l-pyrrolidinyl)-l-naphthylgroup, a 2,6,7,7atetrahydro-5-(1-pyrrolidinyl)-3-indenyl group; a3-(l-pyrrolidinyl)-2-norbomen-2-yl group; and a 3-( l-pyrrolidinyl)-2-indenyl group; and Q represents the non-metallic atoms to complete anitrogen containing heterocyclic ketomethylene nucleus having from fiveto six atoms in the heterocyclic nucleus.

8. A light-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said O represents thenon-metallic atoms necessary to complete a rhodanine nucleus, andwherein said D represents a 2,3,4,4a,5 ,6-hexahydro-7-( 1-pyrrolidinyl)-l -naphthyl group.

9. A light-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said O represents thenon-metallic atoms necessary to complete a rhodanine nucleus, andwherein said D represents a 2,6,7,7a-tetrahydro-5-( lpyrrolidinyl)-3-indenyl group.

10. A light-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said O represents thenon-metallic atoms necessary to complete an isoxazolone nucleus, andwherein said D represents a 2,6,7,7a-tetrahydro-5-(l-pyrrolidinyl)-3-indenyl UNITED STATES PATENT orries CEHNCATE F CQCHNPatent No. 3, 655, 392 Dated Ap il 11 lQYZ Inventor) Arthur Fumia, Jr.and Leslie C-.S Brooker It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

molumn 2, line 5, delete 5,6l'lexahydro and insert 1 ---5,6-hexahydro.

Column 2, line 29, delete "alkoxy-alkyl" and insert --alkoxyalk;yl-.

Column 2, line 30, delete "car-boxyalkyl" and insert --carboxyalkyl.

Column 1, line 57, delete hetrocyclic" and insert ---heterocyclic-.

Column 2, line 62, delete "methoxynaphtoh" and insert---methoXynaphtho-.

Column 2, line 68, delete "benzoXa-zole" and insert ---benzoXazole---.

Column 2, line 69, delete "phenylbenzoX-azole" and insert--phenylbenzoxazole-.

Column 2, line 70, delete "di-methylbenzoxazole" and insert---dimethylbenzoXazole--.

Column 3, line 12, delete "dimethylinolenine and insert--dimethylindolenine-.

Column 3, line 22, delete "pyrazoline" and insert -pyrazolin--.

Column 3, line 2%, delete "benxothiazolyl" and insert benzothiazolyl-.

Column 3, line 50, delete "2thio and insert ---2'-thio--- Page 2 PatentNo. qffiq qog Dated April 11, 1972 Inventor) Arthur Fumia, Jr. andLeslie G. S. Brooker It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

C olumn 3, line 60, delete "thiazolidinedione" and insert---thiazolidinone--.

Column 3, line 61, delete "thiazoline" and insert ---thiazolin-.

Column 3, line 62, delete "thiazoline" and insert ---thiazolin---,

Column A, line 2, delete "l,l,3-diethyl" and insert --l,3diethyl-.

Column l, line 6, delete "imidazolinl" and insert ---imidazolin-.

Column L, line 28, delete "l(3,3a" and insert --l-(3,3a

Column 7, line LO, delete "iden" and insert --inden-- and delete"pyrrolidone" and insert ---pyrrolidine---,

Column 8, line LO, delete "isoxazoline" and insert --isoXe.zolin-.

Column 8, line 69, delete "pyrazoline" and insert --pyraZolin-.

Column 9, line 18, delete 2,7" and insert ---2.7---.

Column 10, lines 3-15, the compound name and structural formula shouldread as follows:

--- l-ethyl-2-{2-/-(l-pyrrolidinyl)2-norbornen-2-yl7vinyl} naphthol,2-d7thiazolium perchlorate P0-1050 UNITED STATES PATENT OFFICECERTIFICATE OF CORRECTTQN Patent No. 3,655,392 Dated April ll, 1972lnventofls) Arthur Fumia, Jr. and Leslie G.S. Brooker It is certifiedthat error appears in the above-identified patent and that said LettersPatent are hereby corrected as shown below:

and compound names The formulas/in Examples l2, 13, 1M, and 15 shouldappear in Examples 13, ll, 15 and 16 respectively.

The substituted formula for Example 14 should read as follows:

C 2H. 5 The substituted compound name for Example 16 should read:deleting thiazoliumr and inserting ---thiazolium--.

Column ll, line 6A, delete overage" and insert ---coverage---.

Column 13, line Bl, delete "tetra-hydro" and insert --tetrahydro---.

Column 13, line 56, delete "pyrrolindine and insert ---pyrrolidine.

Column 1 line 30, delete L" and insert 3--.

Column 15, line 5, delete pyrazoline" and insert ---pyrazolin-- 227 3UNITED STATES PATENT OFFICE CERTIFECATE OF C0 ECTiN Patent No. 3,655,392Dated April 11, 1972 Inventor) Arthur Fumia, Jr. and Leslie G.S. BrookerIt is certified that error appears in the above-identified patent andthat said Letters Patent are hereby corrected as shown below:

Column 15, line 15, delete "2,-6,7,7a" and insert ---2,6,7,7e

Column 15, line 20, delete "3-linde-" and insert B-inde- Column 15, line22, delete 2,6,7,7 5 and insert ,7,7a-tetrahydro-5- Column 16, line 7,delete "3(1-" and insert 3-(1- Column 16, lines 8-10, delete "3-eth 1-2-2-541- pyrrolidinyl) -2-indeny l 7vinyl benzoxazoli m perchlorate;"

Column 16, line 10, delete "pyrolidinyl" and insert ---pyrrolidinyl.

Signed and sealed this 12th day of Septembert 1972.

(SEAL) Attest:

EDWARD M.FLETCHER,JR. ROBERT GOTTSCHALK Attesting Officer Commissionerof Patents

2. A light-sensitive photographic silver halide emulsion spectrallysensitized with a methine dye having at least one of the followingformulas:
 3. A light-sensitive photographic silver halide emulsionspectrally sensitized with a methine dye represented by the followingformula: wherein n represents a positive integer of from 1 to 2; mrepresents a positive integer of from 1 to 3; L represents a methinelinkage; D represents an enamine group selected from the groupconsisting of a 2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthylgroup; a 2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl group; a3-(1-pyrrolidinyl)-2-norbornen-2-yl group; and a3-(1-pyrrolidinyl)-2-indenyl group; R1 represents a member selected fromthe group consisting of an alkyl group and an aryl group; X representsan acid anion; and Z represents the non-metallic atoms necessary tocomplete a heterocyclic nucleus containing from five to six atoms in theheterocyclic ring.
 4. A light-sensitive photographic silver halideemulsion spectrally sensitized with a dye as defined in claim 4 whereinsaid Z represents the non-metallic atoms necessary to complete athiazole nucleus.
 5. A light-sensitive photographic silver halideemulsion spectrally sensitized with a dye as defined in claim 3 whereinsaid Z represents the non-metallic atoms necessary to complete anoxazole nucleus.
 6. A light-sensItive photographic silver halideemulsion spectrally sensitized with a dye as defined in claim 3 whereinsaid Z represents the non-metallic atoms necessary to complete a3,3-dialkylindolenine nucleus.
 7. A light-sensitive photographic silverhalide emulsion spectrally sensitized with a methine dye represented bythe following formula: wherein d represents a positive integer of from 1to 2; L represents a methine linkage; D represents an enamine groupselected from the group consisting of a 2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl group, a2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl group; a3-(1-pyrrolidinyl)-2-norbornen-2-yl group; and a3-(1-pyrrolidinyl)-2-indenyl group; and Q represents the non-metallicatoms to complete a nitrogen containing heterocyclic ketomethylenenucleus having from five to six atoms in the heterocyclic nucleus.
 8. Alight-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said Q represents thenon-metallic atoms necessary to complete a rhodanine nucleus, andwherein said D represents a2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl group.
 9. Alight-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said Q represents thenon-metallic atoms necessary to complete a rhodanine nucleus, andwherein said D represents a2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl group.
 10. Alight-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said Q represents thenon-metallic atoms necessary to complete an isoxazolone nucleus, andwherein said D represents a2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl group.
 11. Alight-sensitive photographic silver halide emulsion spectrallysensitized with dye as defined in claim 7 wherein said Q represents thenon-metallic atoms necessary to complete a 2-pyrazoline-5-one nucleus,and wherein said D represents a 2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl group.
 12. A light-sensitivephotographic silver halide emulsion spectrally sensitized with a methinedye selected from the group consisting of3-ethyl-2-(2-(2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl)vinyl)benzoxazolium iodide;3-ethyl-2-(2-(2,3,4,4a-5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl)vinyl)benzothiazolium iodide;3-ethyl-5-((2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl)methylene)rhodanine;3-ethyl-2-(2,-6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl)benzothiazoliumperchlorate; 3-ethyl-2-(2-(2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl)vinyl)benzoxazolium iodide;3-ethyl-2-(2-(2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl)vinyl)benzothiazolium iodide; 3-phenyl-4-((2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-1indenyl)methylene)-2-ioxzazoline-5-one;3-methyl-1-phenyl-4-((2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl)methylene)-2-pyrazoline-5-one;3-ethyl-5-((2,6,7,7a-tetrahydro-5-(1-pyrrolidinyl)-3-indenyl)methylene)rhodanine;3-ethyl-2-(2-(3-(1-pyrrolidinyl)-2-norbornen-2-yl)vinyl)benzoxazoliumperchlorate;3-ethyl-2-(2-(3-(1-pyrrolidinyl)-2-norbornen-2-yl)vinyl)benzothiazoliumperchlorate;1-ethyl-2-(2-(3-(1-pyrrolidinyl)-2-norbornen-2-yl)vinyl)naphtho(1,2-d)thiazolium perchlorate;1,3,3-trimethyl-2-(2-(3-(1-pyrrolidinyl)-2-indenyl)vinyl)-3H-indoliumperchlorate;3-ethyl-2-(2-(3(1-pyrrolidinyl)-2-indenyl)vinyl)benzoxazoliumperchlorate;3-ethyl-2-(2-(3-(1-pyrrolidinyl)-2-indenyl)vinyl)benzoxazoliumperchlorate;3-ethyl-2-(2-(3-(1-pyrolidinyl)-2-indenyl)vinyl(benzothiazoliumperchlorate and1-ethyl-2-)2-(3-(1-pyrrolidinyl)-2-indanyl)vinyl)naphtho(1,2-d)thiazoliumperchlorate.
 13. A light-sensitive photographic silver halide emulsionspectrally sensitized with3-ethyl-2-(2-(2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl)vinyl)benzothiazolium iodide.
 14. A light-sensitivephotographic silver halide emulsion spectrally sensitized with3-ethyl-5-((2,3,4,4a,5,6-hexahydro-7-(1-pyrrolidinyl)-1-naphthyl)methylene)rhodanine.